A Novel Development for Vapor Phase Alkylation of Aniline Processed with Clay, Oxides and Zeolite
Abstract
Vapour phase catalytic alkylation of aniline with ethanol is carried out over new catalysts including clay (attapulgite, and bentonite), metal oxides (Fe2O3 impregnated on attapulgite, and Fe2O3 + GeO2 supported on attapulgite) and zeolites (ZSM–5) in a down flow reactor. The reaction conditions viz temperature, molar ratio (aniline/ethanol) and catalyst lead to both C– and N–alkylation, with highest conversion of aniline to ethanol at 370°C temperature and 1:6 molar ratio over clay, metal oxides and zeolites catalysts 20%, 53% and 49.35%, 57.62% respectively. Among the tested catalysts, ZSM–5 showed excellent catalytic performance with the highest conversions of 80–98%. The clays were found to be excellent catalysts for N–alkylation of aniline. Further when these clays impregnated with a combination of metal oxides, the activity for C–alkylation of aniline. The main products conversion of aniline to ethanol monoethyl aniline, N, N–diethylaniline, ortho ethylaniline and 2, 6–diethylaniline were formed consecutively.References
M.H. Zeng, Z.Yin, Z.-H. Liu, H.-B. Xu, Y.-C. Feng, Y.-Q. Hu, L.-X. Chang, Y.-X. Zhang, J. Huang, M. Kurmoo, Angew. Chem., Int. Ed. 55 (2016): 11407−11411.
S. Sunwanprasop, T. Nhujak, S. Roengsumran, A. Petsom, Ind. Eng. Chem. Res. 43 (2004):4973–4978.
B. Satyavathi, A.N. Patwari, Bhale Rao, U.T., Process for preparation of a new catalyst useful for producing alkylated aromatic amines. US Patent 6037295, 2000.
M.S. Peters, K. Timmerhaus, W. Ronald, Plant Design and Economics for Chemical Engineers. 5th edition, Mc Graw-Hill USA, 2002.
R. Dwivedi, A. Radhe Shyam, R. Prasad, H.P.S. Chauhan, Alkylation of aniline with ethanol over Zn1xMnxFe2O4 (x= 0, 0.25, 0.50, 0.75 and 1) ferrite system, Ind. J. Chem. Technol., 11 (2004): 254.
K. Sreekumar, T. Mathew, S.P. Mirajkar, S. Sugunan, B.S. Rao, A comparative study on aniline alkylation activity using methanol and dimethyl carbonate as the alkylating agents over Zn–Co–Fe
ternary spinel systems. Appl. Catal. A, 201(2000) L1–L8.
G.D. Yadav, N.S. Doshi, Alkylation of aniline with methyl-tert-butyl-ether (MTBE) and tertbutanol over solid acids: product distribution and kinetics. J. Mol. Catal. A: Chem. 194 (2003):195–209.
Yadav GD. Synergism of clay and heteropoly acids as nano-catalysts for the development of green processes with potential industrial applications. Catalysis Surveys from Asia. 2005;9(2):117-37.
K. Nishamol, K.S. Rahna, S. Sugunan, Selective alkylation of aniline to N-methyl aniline using chromium manganese ferrospinels. J. Mol. Catal. A: Chem. 209 (2004): 89–96.
R. Anand, S.S. Khaire, R. Maheswari, K.U. Gore, V.R. Chumbhale, N-alkylation of aniline with ethanol over HY and dealuminated HY zeolites. Appl. Catal. A, 242 (2003): 171–177.
B. Satyavathi, A.N. Patwari, M. Bhagwanth Rao, Regio-selective catalytic vapour phase alkylation of aniline: preparation of 2,6-diethylaniline, Appl. Catal. A, 246 (2003): 151–160.
H. Li, S. Saravanamurugan, S. Yang, A. Riisager, Catalytic Alkylation of 2-Methylfuran with Formalin Using Supported Acidic Ionic Liquids, ACS Sustainable Chem. Eng. 3 (2015): 3274–3280.
P. Paul, P. Bhanja, N. Salam, U. Mandi, A. Bhaumik, S. Mafiz Alam, Sk. Manirul Islam, Silver nanoparticles supported over mesoporous alumina as an efficient nanocatalyst for N-alkylation of hetero (aromatic) amines and aromatic amines using alcohols as alkylating agent, J. Colloid
Interface Sci. 493 (2017): 206–217.
Md. Hadi Ghasemi, E. Kowsari, Convenient N-Alkylation of amines using an effective magnetically separable supported ionic liquid containing an anionic polyoxometalate, Res. Chem.Intermed. 43 (2017): 1957–1968.
O.A. Ponomareva, P.A. Shaposhnik, M.V. Belova, B.A. Kolozhvari, I.I. Ivanova, Novel method for the preparation of Cs-containing FAU(Y) catalysts for aniline methylation, Front. Chem. Sci. Eng. 12(1) (2018): 70–76.
M. Vellakkaran, K. Singh, D. Banerjee, An Efficient and Selective Nickel-Catalyzed Direct N‑Alkylation of Anilines with Alcohols, ACS Catal. 7 (2017): 8152−8158.
M. Victoria Jiménez, J. Fernández-Tornos, M. González-Lainez, B. Sánchez-Page, F. Javier Modrego, L.A. Oro, J.J. Pérez-Torrente, Mechanistic studies on the N-alkylation of amines with alcohols catalysed by iridiumIJI) complexes with functionalised N-heterocyclic carbine Ligands, Catal. Sci. Technol., 8 (2018): 2381–2393.
J. Das, D. Banerjee, Nickel-Catalyzed Phosphine Free Direct N‑Alkylation of Amides with Alcohols, J. Org. Chem.83(2018):3378−3384.
J.P. Zhong, B. Liu, T. Yang, Y.-J. Liu, Z.-H. Zhu, B.-F. Shi, Mohamedally Kurmoo, and Ming-Hua Zeng, Tracking the Progress and Mechanism Study of a Solvothermal in Situ Domino N‑Alkylation Reaction of Triethylamine and Ammonia Assisted by Ferrous Sulfate, Inorg. Chem. 56 (2017):
−10126.
E.S. Streng, D.S. Lee, M.W. George, M. Poliakoff, Continuous N-alkylation reactions of amino alcohols using γ-Al2O3 and supercritical CO2: unexpected formation of cyclic ureas and urethanes by reaction with CO2, Beilstein J. Org. Chem. 13 (2017): 329–337.
X. Yu, Y. Li, H. Fu, X. Zheng, H. Chen, R. Li, Mechanistic investigation of imine formation in ruthenium‐catalyzed N‐alkylation of amines with alcohols, Appl. Organometal. Chem. 32 (2018):
–7
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